DE1232158B - Process for the preparation of N-pentachlorophenyldiamines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int CL:

Number:
File number:
Filing date ^
Display day:

C07c

C07d

German class: 12q-5

1232158
F45779IVb / 12q
April 9, 1965
January 12, 1967

The present invention relates to a process for the preparation of new N-pentachlorophenyldiamines; the process consists in that one N-Pentachlorphenyldiamine of the formula

Process for the production of
N-pentachlorophenyl diamines

Cl

in which A denotes an alkylene chain containing more than 2 carbon atoms, optionally interrupted by heteroatoms, an arylene group or an unsaturated aliphatic group, and R denotes hydrogen or an optionally substituted alkyl, alkenyl or aralkyl group, with mixtures of formic acid and formaldehyde or its Polymerization products methylated, expediently in the presence of water and with heating to temperatures of about 70 to 100 ^° C. The process products obtained according to the invention is the general formula

Cl Cl

CH ₃

CH ₃

Cl Cl

attributable, in which A has the meaning given above, while Ri is an optionally substituted one Alkyl, alkenyl or aralkyl group.

That in the process according to the invention also the hydrogen atom through the methyl group is replaced, which is located on the nitrogen atom adjacent to the pentachlorophenyl group, is surprising. Because it is known that this nitrogen atom no longer enables salt formation which is considered to be a prerequisite for reductive methylation (cf. J. Org. Chem., 16, Pp. 661 to 721 [1951], and Chemiker-Zeitung, 80, pp. 779 to 781 [1965]). In addition, the Implementation of pentachlorophenylethylenediamine with mixtures of formic acid and formaldehyde the hydrogen atom which is located on the nitrogen atom adjacent to the pentachlorophenyl group is located, is practically not methylated even when heated to temperatures of 100 ° C.

The N-Pentachlorphenyldiamine to be methylated can in bulk or in the form of solutions in inert, water-immiscible solvents, applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Werner Daum, Krefeld-Bockum

z. B. xylene, or in higher-boiling alcohols such as butanol, to formic acid and formaldehyde or its polymerization products are given to existing mixtures. For larger approaches it may be useful to submit only part of the methylating agent and the others Part of flowing in at the same time as the N-pentachlorophenyldiamines.

As for the amounts of formic acid and formaldehyde or its polymerization products, it is generally sufficient if, for each methyl group to be introduced, little more than the stoichiometric amount of formaldehyde is used, while formic acid is expediently used an excess is applied. If desired, in addition to formic acid, other carboxylic acids, such as acetic acid, or acid salts, such as alkali hydrogen sulfates, are present in the reaction mixture be; the reaction can also be carried out in the presence of alkali metal forms.

The methylation products obtained in the process according to the invention can be obtained by distillation in a high vacuum, by crystallization at low temperatures or by recrystallization their mineral acid salts are purified.

The new N-pentachlorophenyldiamines of the present invention are intermediates for the Manufacture of pesticides or pharmaceutical products.

example 1

56 g of N-pentachlorophenyl-tetramethylenediamine (0.166 mol) are added in the course of 30 minutes a mixture of 69 g of 98% formic acid (1.47 mol) and 50 g of 35% formaldehyde solution, kept at 90 ° C (0.58 M9I). The reaction mixture is allowed to stand for 12 hours, then

609 757/408

cooled and mixed with a solution of 65 g of sodium hydroxide in 500 ml of water. The reaction product which separates out as an oily phase is separated from the reaction mixture by extraction twice with 100 ml of cyclohexane each time and the entire cyclohexane solution is washed with water, dried over sodium hydroxide and evaporated. The yield of crude N ¹ , N ¹ , N ² -trimethyl-N ² -pentachlorophenyl-tetramethylenediamine is 55 g. 45.5 g of a fraction passing over at 149 to 152 ° C./0.04 torr can be obtained by distillation. In the IR spectrum of the distillate, no> N - Η band is visible at 2.9 to 3.1 μ. Carbon found: 40.91%, calculated: 41.24%.

B e i s ρ i e 1 2

A solution of 109.4 g of N-pentachlorophenylhexamethylenediamine (0.3 mol) in 163 ml of xylene is added over 40 minutes to a mixture of 80 g of 98% strength formic acid (1.70 mol) and 94 g, which is kept at 84 to 90.degree 35% formaldehyde solution (1.1 mol) was added, kept at 90 ° C. for a further 5 hours and then treated with 700 ml of water. The upper xylene-containing phase is then removed, the aqueous phase is made alkaline and extracted with cyclohexane. The cyclohexane-containing solution gives 115 g of crude N ^ N ^ N-trimethyl-N ^ pentachlorophenyl-hexamethylenediamine in the work-up explained in Example 1; 108.5 g of a purified product with a boiling point of 160 ^: C / 0.02 Torr can be obtained from this by distillation. The yield of purified product is 89%, based on N-pentachlorophenyl-hexamethylenediamine. The distillate shows no> N - H bands in the IR spectrum at 2.9 to 3.1 μ. Carbon found: 44.26%, calculated: 44.3%.

Example 3

109.4 g of N-pentachlorophenyl-hexamethylenediamine (0.3 mol) are added over 20 minutes to a mixture of 97.5 g of 98% strength formic acid (2.15 mol) and 32.5 g of paraformaldehyde kept ^{at 80: C} (1.08 moles). The reaction mixture is then held at 80 to 90 ^° C. for a further 5 hours. If the reaction mixture is worked up as described in Example 1, 114 g of N ^ N ¹ , N ² - trimethyl - N ² - pentachlorophenylhexamethylenediamine are obtained.

Example 4

50

323 g of N-pentachlorophenylhexamethylenediamine are added to a mixture of 317 g of 98% strength formic acid (6.75 mol), 340 g of 35% strength formaldehyde solution (3.97 mol), 150 ml of water and 216 g of sodium bisulfate (0.887 moles). The reaction mixture is then heated to 90 ° C. and kept at this temperature for 12 hours. Working up gives 298 g of N ^ N ^ N ^ trimethyl-N ² -pentachlorophenyl-hexamethylenediamine.

60 Example 5

165.5 g of N ¹ -benzyl-N ² -pentachlorophenyl-hexamethylenediamine (0.364MoI) are in the course of 9 minutes in a heated to 80 ° C mixture of 85.5 g of 98% formic acid (1.82 mol) and 69 g 35% formaldehyde solution (0.8 mol) was added dropwise. The reaction mixture is then ^{kept at 88 °} C. for a further 4 hours. Working up gives 165.5 g of crude N ¹ -benzyl-N ¹ , N ² -dimethyl-N ² -pentachlorophenyl-hexamethylenediamine. 155.5 g of a fraction boiling in the range from 213 to 217 ° C./0.01 Torr, which does not show any> N - Η band in the IR spectrum, can be obtained from this by distillation. The analysis values are 53.02% for carbon, 36.9% for chlorine and 5.63% for nitrogen, the calculated values are 52.25% for carbon, 36.72% for chlorine and 5.80% for nitrogen.

The following experiment shows that when pentachlorophenylethylenediamine is reacted with mixtures of formic acid and formaldehyde, the hydrogen atom on the nitrogen atom adjacent to the pentachlorophenyl group is ^{practically not methylated even when heated to temperatures of 100 ° C.}

346 g of N-pentachlorophenyl-ethylenediamine (1.12 mol) were in the course of 20 minutes in a ^{mixture kept at 90 0} C of 485 g of 98% formic acid (10.3 mol) and 380 g of 35% formaldehyde solution (4.43 Mole). The reaction mixture was left to stand for 12 hours, then cooled, and a solution of 350 g of sodium hydroxide in 1500 ml of water was added. The reaction product separating out as an oily phase was separated from the reaction mixture by extracting twice with 500 ml of cyclohexane each time, and the entire cyclohexane solution was then washed with water, dried over sodium hydroxide and evaporated. The yield of the crude methylation product was 369 g. When distilling in small portions, 93% of a non-uniform distillate passing over at 156 to 165 ° C./0.25 torr could be obtained. The IR spectrum showed a pronounced band at 2.96 μ, which indicated the presence of compounds with a> N - H group. The analysis values were 36.46% for carbon and 8.23% for nitrogen. The values calculated for N ¹ ^ -dimethyl-N ² -pentachlorophenyl-ethylenediamine are 35.7% for carbon and 8.33% for nitrogen, the values calculated for N ^ N ^ N ² -trimethyl-N ² -pentachlorophenyl-ethylenediamine for carbon 37.65% and for nitrogen 8.0%.

Claims (1)

Claim: Process for the production of N-pentachlorophenyldiamines, characterized in that N-Pentachlorplienyldiamine the formula Cl Cl Cl Cl in which A is an optionally by heteroatoms, an arylene radical or an unsaturated aliphatic Radical is interrupted alkylene chain containing more than 2 carbon atoms and R stands for hydrogen or for an optionally substituted alkyl, alkenyl or aralkyl group with mixtures of formic acid and formaldehyde or its polymerization products methylated. 609 757/408 1.67 ® Bundesdruckerei Berlin